In a joint press conference on Tuesday, Premiers Daniel Andrews and Dominic Perrottet said the general practitioner-partnered services will handle issues such as mild infections, fractures and burns.
Services will operate for extended hours and patients will not be charged for services provided by GPs, including those without a Medicare card.
These new services will be commissioned in partnership with primary health networks to set them up in places of highest demand.
Victoria has previously announced five of the clinics, while NSW has five operating in Sydney as part of 13 committed by the federal government.
The extra centres, once progressively opened, will bring the total number across the two states to 50.
"It's never been harder to find a bulk-billing appointment with a doctor than it is right now. And instead of complaining about it, we're doing something about it," Mr Andrews told reporters at the Olivia Newton-John cancer centre.
In Victoria, 10 centres will be established to partner with hospitals at Frankston, Bendigo, Casey, Albury Wodonga, Dandenong, Latrobe, Werribee Mercy Box Hill and the Austin and Alfred hospitals.
Another 10 Victorian locations will be announced soon, along with the NSW locations.
Mr Andrews said Victoria's 20 extra urgent care clinics would cost the state $70 million, but represented value for money.
"This is just common sense. It's not a cost, it's an investment in a better primary care system for families, for patients and communities right across our state," he said.
Mr Perrottet said the states were not "going to pass the buck and shift the blame to the federal government, but we need to work on it".
"If we can't reform the health system after a one-in-100-year event then we never will," he said.
"What has become very clear over time, prior to the pandemic and during, is that there is no health system that is immune from pressure."
NSW emergency departments see more than three million patient presentations a year.
In the first quarter of 2022, there were 734,704 attendances at NSW emergency departments, with hospitals throughout the state continuing to experience sustained, high demand for emergency care.
Victorian emergency departments have been the busiest ever, with presentations hitting a record 486,701 in the most recent quarter.
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